Structural changes accompanying stabilization and carbonization processes of the two types of polyacrylonitrile (PAN) nanofiber precursors (pure PAN and PAN with carbon nanotubes) were studied using infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The fibrous membranes were preliminary stabilized in air followed by the two-step carbonization process under nitrogen atmosphere. IR absorption spectra showed that the introduction of a small amount of functionalized multiwall carbon nanotubes (MWCNT) into the PAN precursor has a significant impact on its stabilization process. Raman spectroscopy study showed that the structure of carbon nanofibers containing CNT is distinctly more ordered in comparison to pure carbon nanofibers. Based on the XPS analysis the concentration of heteroatoms and the type and amount of functional groups on the surfaces of both types of nanofibers were determined. The results indicate a high potential of functionalized MWCNT as a pyrolysis modifier of polymer precursor leading to the formation of carbon nanofibers with controlled structure and defined chemical state of the surface. (C) 2016 Elsevier B.V. All rights reserved.